Silanol composition, cured product, and adhesive

Abstract

To provide a silanol composition which has excellent adhesive strength and transparency when cured. The present invention provides a silanol composition in which the ratio of cyclic silanol (A1) represented by formula (1) and its stereoisomers is controlled. JPEG2023036679000031.jpg40170 (In formula (1), R 1 ~R 4 are each independently a fluorine atom, an aryl group, a vinyl group, an allyl group, a fluorine-substituted linear or branched alkyl group having 1 to 4 carbon atoms, or an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms.

Description

[Technical Field]

[0001] The present invention relates to a silanol composition, a cured product, and an adhesive. [Background technology]

[0002] Cyclic silanols are compounds with a skeleton that forms a ring structure through siloxane bonds. A curable composition containing such a compound (also called a "silanol composition") exhibits a light-emitting property. It is used for protecting, sealing, and adhering semiconductor elements such as diode elements. The lens can change or adjust the wavelength of the light emitted from the light emitting diode element. It is used for purposes such as

[0003] In recent years, cyclic silanols with precisely controlled structures have been reported. discloses all-cis tetrahydroxytetramethyltetracyclosiloxane. It has been done. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Inorganic Chemistry Vol.49, No.2, 2010, 572‐577. Summary of the Invention [Problem to be solved by the invention]

[0005] However, when the curable composition containing all-cis tetrahydroxytetramethyltetracyclosiloxane disclosed in Non-Patent Document 1 is applied to an object to be protected, sealed, or bonded, there is a problem that sufficient adhesive strength is not obtained. Furthermore, when cyclic silanols and compositions containing such cyclic silanols are applied to optical materials such as lenses, transparency is required when the cyclic silanols and compositions containing such cyclic silanols are cured.

[0006] Therefore, an object of the present invention is to provide a silanol composition that has excellent adhesive strength and transparency. Here, "adhesive strength" refers to adhesive strength when cured, and "transparency" encompasses both transparency in the form of the composition and transparency in the form of the cured composition. [Means for solving the problem]

[0007] As a result of intensive research into solving the above-mentioned problems, the present inventors discovered that the above-mentioned problems can be solved by adjusting the ratio of each stereoisomer of cyclic silanol to a specific range, thereby completing the present invention. That is, the present invention is as follows.

[0008] [1] Cyclic silanol (A1) represented by the following formula (1): [ka] (In formula (1), R 1 ~R 4 are each independently a fluorine atom, an aryl group, a vinyl group, an allyl group, a linear or branched alkyl group having 1 to 4 carbon atoms substituted with fluorine, or an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms), in the presence of water, weak A step of reacting with an acid; a step of removing crystalline precipitates by adding a poor solvent or cooling the solution of the obtained product in a good solvent after the step of reacting with the weak acid, thereby obtaining a solution of the soluble portion; A method for producing a silanol composition comprising: [2] The method for producing a silanol composition according to [1], wherein the cyclic silanol (A1) is a single isomer or a mixture of isomers. [3] The method for producing a silanol composition according to [2], wherein the cyclic silanol (A1) includes an all-cis type, a cis-trans-cis type, a trans-trans-cis type, or an all-trans type. [4] The haze of the silanol composition at a thickness of 3 μm is 10% or less. [1]~[ 3 10. A method for producing a silanol composition according to any one of the preceding claims. [5] The silanol composition comprises cyclic silanols (B1) to (B4) represented by the following formulas (2) to (5): [ka] [ka] [ka] [ka] (In formulas (2) to (5), R 1 ~R 4 are each independently a fluorine atom, an aryl group, a vinyl group, an allyl group, a linear or branched alkyl group having 1 to 4 carbon atoms and substituted with fluorine, or an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, When the proportions (mol %) of the cyclic silanols (B1), (B3), and (B4) relative to the total amount of the cyclic silanols (B1) to (B4) are a, c, and d, respectively, the following relationship is satisfied: (x)75≦a+c<100 (y)75≦c+d<100 and 25 <d<100 (z)60≦c<100 [1] to [ 4 10. A method for producing a silanol composition according to any one of the preceding claims. [6] When the ratio (mol %) of the cyclic silanol (B2) to the total amount of the cyclic silanols (B1) to (B4) is represented by b, the following condition (w) is satisfied: (w)0 <b≦20 fulfill, [ 5 ] A method for producing a silanol composition according to the present invention. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a method for producing a silanol composition that changes the positional relationship between the organic group R and the hydroxy group on the silicon atom of the cyclic siloxane skeleton. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows the H-NMR spectrum used to calculate the stereoisomer ratio of the silanol composition obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as "the present embodiment") will be described in detail. Note that the present invention is not limited to the present embodiment, and various modifications can be made within the scope of the gist of the present invention. The method for producing the silanol composition of this embodiment includes the steps of: 1 ~R 4 and each independently represent a fluorine atom, an aryl group, a vinyl group, an allyl group, a linear or branched alkyl group having 1 to 4 carbon atoms substituted with fluorine, or an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms), with an acid in the presence of water; It has. According to the production method of this embodiment, a silanol composition can be obtained that changes the positional relationship between the organic group R and the hydroxy group on the silicon atom of the cyclic siloxane skeleton.

[0012] (Silanol composition) The silanol composition of the present embodiment contains a cyclic silanol (A1) represented by the following formula (1): Contains.

[0013] [ka]

[0014] In formula (1), R 1 ~R 4 each independently represents a fluorine atom, an aryl group, a vinyl group, an allyl group, a fluorine-substituted linear or branched alkyl group having 1 to 4 carbon atoms, or an unsubstituted It contains a substituted, straight-chain or branched alkyl group having 1 to 4 carbon atoms.

[0015] The cyclic silanol (A1) is a cyclic silanol (B1) represented by the following formulas (2) to (5): ) to (B4). [ka] [ka] [ka] [ka]

[0016] In formulas (2) to (5), R 1 ~R 4 each independently represents a fluorine atom, an aryl group, or a vinyl group. an allyl group, a linear or branched alkyl group having 1 to 4 carbon atoms substituted with fluorine, or is an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. The silanol is an organic group R on silicon. 1 ~R 4 and stereoisomers derived from the configuration of the hydroxyl groups In this embodiment, the cis and trans cyclic silanols respectively refer to adjacent Two hydroxy groups or two adjacent R 1 ~R 4 One of the groups is attached to the cyclic siloxane skeleton. The two adjacent hydroxy groups or the two adjacent R groups are in the same orientation (cis). This means that the two are in different orientations (trans) relative to the cyclic siloxane skeleton.

[0017] The silanol composition of this embodiment contains cyclic silanols (B1) to (B4) in an amount of 1:1 or more based on the total amount of the cyclic silanols (B1) to (B4). The proportions (mol %) of the cyclic silanols (B1), (B3), and (B4) are respectively , c, and d, the following conditions (x), (y), and (z); (x)75≦a+c<100 (y)75≦c+d<100 and 25 <d<100 (z)60≦c<100 At least one selected from the group consisting of:

[0018] The silanol composition of this embodiment has excellent adhesive strength and transparency when cured. The reason why the silanol composition of this type has excellent adhesive strength and transparency is thought to be as follows.

[0019] The cyclic silanols (B1) to (B4) each have high crystallinity, and the silanol composition The precipitation of microcrystals reduces the smoothness of the bonding surface to which the silanol composition is applied. The adhesion deteriorates. Further, due to the presence of a partial crystalline component in the silanol composition, light scattering occurs and the transparency deteriorates. In contrast, the silanol composition of the present embodiment becomes amorphous by the ratio of the cyclic silanols (B1) to (B4) satisfying a predetermined condition, and excellent adhesion and transparency are exhibited. However, the above reasons do not limit the mechanism of the manifestation of adhesion and transparency.

[0020] From the viewpoint of further excellent adhesion and transparency, the condition (x) in the present embodiment is preferably 75 ≦ a + c ≦ 95, and more preferably 75 ≦ a + c ≦ 90. From the viewpoint of further excellent adhesion and transparency, the condition (y) in the present embodiment is preferably 75 ≦ c + d ≦ 95 and 25 < d ≦ 95, and more preferably 75 ≦ c + d ≦ 90 and 25 < d ≦ 90. From the viewpoint of further excellent adhesion and transparency, the condition (z) in the present embodiment is preferably 60 ≦ c ≦ 95, and more preferably 60 ≦ c ≦ 90.

[0021] As a method for satisfying at least one of the conditions (x), (y), and (z), as described above, for example, a method of controlling the ratio of the cyclic silanol (B2) can be mentioned. The control of the ratio of the silanol (B2) will be described in detail in the method for producing the silanol composition described later. For example, isomerization of the cyclic silanol represented by the formula (1) obtained by a specific method is performed, the crystals of the silanol (B2) are removed, or a method combining them can be mentioned. [[ID=�4]]For example, isomerization of the cyclic silanol represented by the formula (1) obtained by a specific method is performed, the crystals of the silanol (B2) are removed, or a method combining them can be mentioned. For example, isomerization of the cyclic silanol represented by the formula (1) obtained by a specific method is

[0022] From the viewpoint of obtaining a highly transparent silanol composition, the silanol composition of the present embodiment is The ratio of the cyclic silanol (B2) to the total amount of the cyclic silanols (B1) to (B4) (in mol %) is preferably b, and the following condition (w): 0 < b ≦ 20 is satisfied. Above For the condition (w), it is more preferably 0 < b ≦ 18, and even more preferably 0 < b ≦ 15.

[0023] As a method for setting the condition (w) to 0 < b ≦ 20, as described above, for example, time control of the isomerization reaction , or crystal removal of the silanol (B2) by a recrystallization operation, or a method combining them can be mentioned.

[0024] In the silanol composition of this embodiment, a, b, c, and d can be 1 calculated from 1H-NMR. When measuring the 1H-NMR of the cyclic silanol (A1) contained in the silanol composition of this embodiment 1 , for example, when R 1 ~R 4 are all methyl groups, the signals of the methyl group hydrogens of the cyclic silanol ( A1) are, from the high magnetic field side, all-cis type (B1), tra ns-trans-cis type (B3), trans-trans-cis type (B3), c is-trans-cis type (B2), all-trans type (B4), trans-t rans-cis type (B3) in this order, and a total of 6 peaks of 4 isomers are observed. From the integration values of such hydrogens, the respective ratios a, b, c, and d of the cyclic silanols (B1) to (B4) are calculated.

[0025] Examples of the aryl group in this embodiment include a phenyl group, a naphthyl group, etc.

[0026] ​In this embodiment, the fluorine-substituted linear or branched alkyl group having 1 to 4 carbon atoms Examples of the alkyl include the following groups: CF3-, CF3CF2-, CF3CF2CF2-, (CF3)2CF-, CF3CF2CF2CF2-, HCF2CF2CF2CF2-, (CF3)2CFCF2-

[0027] In this embodiment, the unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms includes is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Examples include tert-butyl.

[0028] R in this embodiment 1 ~R 4 The groups are each independently preferably unsubstituted, linear or branched. It is an alkyl group having 1 to 4 carbon atoms.

[0029] The silanol composition of this embodiment has a haze of 10% or less at a thickness of 3 μm. It is preferable that the haze of the silanol composition is 10% or less. The transparency at the time of application tends to be higher and the adhesive strength tends to be better. or 5% or less, more preferably 2% or less, and even more preferably 1% or less. Below.

[0030] As a method for reducing the haze of the silanol composition to 10% or less, for example, a method for reducing the haze of the silanol composition to 10% or less can be carried out by using a compound represented by the formula (1) By adjusting the ratio of isomers in the cyclic silanol (A1) represented by or a method of reducing the amount of metal contained in the composition.

[0031] Specifically, the haze of the silanol composition can be measured by the method described in the examples. can be done.

[0032] The synthesis of cyclic silanols by oxidation of cyclic hydrosilane compounds using metal catalysts In this case, there is a concern that residual transition metals derived from the metal catalyst may remain. For example, coloration occurs due to the reduction of residual metal ions when exposed to high-energy light such as ultraviolet light. The silanol composition of the present embodiment is prepared as described in the production method to be described later. It can be produced by a method that does not leave any transition metal residue, i.e., a method that does not use a metal catalyst. Therefore, coloring caused by irradiation with a low-pressure mercury lamp or the like tends to be suppressed.

[0033] In addition, since transition metals generally have large absorption coefficients, the presence of trace amounts of residual metal ions is difficult to detect. This causes a decrease in the light transmittance of the silanol composition. As mentioned above, by eliminating the residual transition metal ions (i.e., the silanol composition Since the material does not contain transition metals, the decrease in light transmittance is suppressed, and light transmittance in the ultraviolet region is improved. The silanol composition of the present embodiment has a wavelength of 1000 nm at a thickness of 3 μm. The light transmittance at 265 nm is preferably 75% or more, and more preferably 78% or more. The light transmittance of the silanol composition is measured by the following method. This can be done by the method described in the Examples.

[0034] Therefore, from the viewpoint of increasing the light transmittance of the silanol composition and irradiating it with a low-pressure mercury lamp, etc. From the viewpoint of suppressing coloration due to the presence of the transition metal, the ratio of the transition metal in the silanol composition of the present embodiment is Preferably, it is less than 1 ppm by mass, more preferably less than 1 ppm by mass, based on the total weight of the silanol composition. It is preferably less than 0.5 ppm by mass, more preferably 0 ppm by mass (i.e., silanol groups). The composition does not contain a transition metal. Examples of the transition metal include palladium. It can be obtained.

[0035] The silanol composition of the present embodiment contains a cyclic silanol (A1) represented by the following formula (1): and may further contain a dehydration condensate (A2) of the cyclic silanol (A1). In the measurement by gel permeation chromatography, the surface of the dehydrated condensate (A2) The area of ​​the cyclic silanol (A1) and the dehydration condensate (A2) is 0% or less relative to the total area of ​​the cyclic silanol (A1) and the dehydration condensate (A2). It is preferable that the excess is not more than 50%.

[0036] The dehydration condensation product of the cyclic silanol represented by formula (1) is a cyclic silanol represented by formula (1). At least one of the silanol groups of the silanol is represented by at least one other silanol group represented by formula (1). and at least one silanol group in the cyclic silanol molecule of It is a compound obtained by a bond-forming reaction.

[0037] The dehydration condensation product of the cyclic silanol represented by formula (1) can be, for example, represented by the following formula (7): It can be expressed as:

[0038] [ka]

[0039] In formula (7), four R's are each independently the same as R's in formula (1). 1 ~R 4 Either Fluorine atom, aryl group, vinyl group, allyl group, linear or branched chain substituted with fluorine unsubstituted linear or branched alkyl having 1 to 4 carbon atoms; and m is an integer of 2 or more. The silanol group may be any silanol group. In the compound, two or more siloxane bonds are formed between two or more cyclic silanol structures. In addition, preferred groups for R in formula (7) include R 1 ~R 4 Similar to the base Examples of suitable groups include:

[0040] Specific examples of the dehydration condensation product of cyclic silanol represented by formula (1) include the following compounds: However, the dehydration condensation product of the cyclic silanol represented by formula (1) is the following compound: In addition, the cyclic silanol skeleton in the following compounds is not limited to the following. The orientation of the hydroxy group (-OH) and the R group is not limited. are each independently R in formula (1). 1 ~R 4 Furthermore, the following compounds are Preferred groups for R in the formula are R 1 ~R 4 The same preferred groups as those mentioned above can be mentioned.

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] The dehydration condensation product of cyclic silanol represented by formula (1) was obtained by gel permeation chromatography. The molecular weight calculated by the measurement of the roughness is preferably 500 to 1,000,000. It is more preferably 500 to 100,000, and even more preferably 500 to 10,000. It is 00.

[0047] The silanol composition of this embodiment is suitable for measurement by gel permeation chromatography. wherein the area of ​​the dehydration condensation product (A2) is the area of ​​the cyclic silanol (A1) and the dehydration condensation product (A2). It is preferable that the gel permeation rate is more than 0% and 50% or less of the total area of ​​the mixture (A2). The area of ​​each compound determined by ion chromatography is The content of each compound in the composition is shown.

[0048] When the area of ​​A2 is more than 0% and 50% or less, the silanol composition is produced. The viscosity does not become too high, and the organic solvent or water is removed from the silanol composition containing the organic solvent or water. The area of ​​A2 is more preferably more than 0% and 40% or less, and even more preferably More preferably, it is more than 0% and 25% or less.

[0049] The area of ​​A2, i.e., the content of A2, is determined by, for example, the amount of ring When cyclic silanol (A1) is obtained by isomerization of cyclic silanol (B1) with acid, The acidity can be controlled by the type of acid used in the activation reaction.

[0050] The areas of A1 and A2 by gel permeation chromatography, i.e., A1 The content of A2 can be specifically measured by the method described in the Examples.

[0051] (Method of producing silanol composition) The silanol composition of the present embodiment may be, for example, a cyclic silanol represented by formula (1) It can be prepared by reacting it with an acid in the presence of water. When acid acts on cyclic silanol, an isomerization reaction occurs, and the silicon in the cyclic siloxane skeleton is The positional relationship between the organic group R and the hydroxy group on the substrate changes.

[0052] The acid is not particularly limited, but examples thereof include inorganic acids such as hydrochloric acid and phosphoric acid, and trifluoroacetic acid. Organic acids such as fluoromethanesulfonic acid and acetic acid can be used. From the viewpoint of suppressing condensation and controlling the stereoisomer composition, it is preferable to use a weak acid, and acetic acid is It is more preferable to use

[0053] The cyclic silanols prepared by the isomerization reaction may be any single isomer or a mixture of isomers. Even when a compound is used, the all-cis type and cis type represented by the above formulas (2) to (5) can be used. -trans-cis, trans-trans-cis, all-trans Cyclic silanols (B1) to (B4) are included.

[0054] The cyclic silanol represented by formula (1) used in the preparation of the silanol composition of this embodiment is For example, in the presence of a base, a monomeric trialkoxysilane represented by formula (8) is hydrolyzed to The cyclic silane represented by formula (1) can be synthesized by a manufacturing method including the step of The method for synthesizing the cyclic silanol is to hydrolyze the cyclic silanol represented by formula (9) and then add the metal silanol to the cyclic silanol. After obtaining the salt, it is preferable to include a step of treating with an acid. The metal salt of the cyclic silanol represented by formula (9) can be obtained from realkoxysilane by Inorganic ic Chemistry Volume 49, Issue 2, P572-57 It can be synthesized according to the method described in 7.

[0055] [ka]

[0056] In formula (8), R represents a fluorine atom, an aryl group, a vinyl group, an allyl group, or a fluorine-substituted group. a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or an unsubstituted straight-chain or branched alkyl group having 1 to 4 carbon atoms; R is a branched alkyl having 1 to 4 carbon atoms. a , R b , and R c are each independently an organic group. There are no particular limitations on the type of alkyl group, and preferably the alkyl group is an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. It's a kill.

[0057] In formula (9), R 1 ~R 4 Each independently represents the same as R, and each independently represents lithium. ions, sodium ions, potassium ions, rubidium ions, and cesium ions, etc. It is any one selected from the group consisting of:

[0058] Examples of alkalis used for hydrolysis include sodium hydroxide and potassium hydroxide. Any hydroxide can be used, but it is preferable to use a hydroxide which is easy to purify by recrystallization after the reaction. From this viewpoint, it is preferable to use sodium hydroxide or potassium hydroxide.

[0059] The metal salt of the cyclic silanol represented by the formula (9) can be converted into a compound by the action of an appropriate acid. The neutralization reaction results in a cyclic silanol represented by formula (1). For example, inorganic acids such as hydrochloric acid and organic acids such as acetic acid can be used. From the viewpoint of suppressing dehydration condensation of crystalline silanols, it is desirable to use acetic acid. In the method for producing the silanol composition, a metal salt of a cyclic silanol represented by formula (9) is used as a starting material. It is used as a compound, and when an acid is applied, it is converted into a cyclic silanol represented by formula (1) and isomerized. The reaction may be carried out simultaneously.

[0060] The cis-trans-cis cyclic silanol (B2) represented by formula (3) is This phenomenon is due to the cis-trans-cis ring structure. This is thought to be due to the high crystallinity of the silanol (B2), and This is particularly noticeable when the silanol (B2) is removed. This makes it possible to obtain a silanol composition having excellent transparency and adhesive strength.

[0061] In the isomerization reaction, the amount of acid to be converted and the reaction time are controlled to obtain a cyclic silanolate. The amount of cyclic silane (B2) can be adjusted to be low. The alcohol (B1) is added with 0.1 to 3.0 mol / L, preferably 0.8 to 2.0 mol / L of When 0.5 to 10 equivalents, preferably 1.0 to 3.0 equivalents of an aqueous acetic acid solution are applied, At the same time, the proportion a of cyclic silanol (B1) in the silanol composition decreases, and The proportion of silanol (B3) (c) increases. After 3.5 hours of reaction, the proportions a and b c becomes almost equal, and after 5 hours the proportion a decreases to about 30%.

[0062] In addition, when cyclic silanol (B4) was treated with an aqueous solution of acetic acid, As d decreases, the ratio c increases. When the liquid is applied, the ratio c decreases, while the ratio a, the ratio b, and the ratio d increase. do.

[0063] In order to obtain a silanol composition with high transparency, the proportion of cyclic silanol (B2) is reduced. It is preferable to suppress the proportion of the cyclic silanol (B2) as much as possible. , time control of the isomerization reaction, or crystal removal of silanol (B2) by recrystallization, or More specifically, the isomerization reaction of cyclic silanol In the stage where the amount of cyclic silanol (B2) produced is small, or ) is used as the starting material, the isomerization reaction proceeds sufficiently, and the reaction is completed when the ratio of After stopping the reaction, a poor solvent is added to the resulting solution of the product in the good solvent and the mixture is cooled. The cyclic silanol (B2) precipitates as crystals. The cyclic silanol (B2) in the silanol composition was removed and the solution of the soluble portion was concentrated. ) can be reduced to obtain a silanol composition with high transparency.

[0064] When performing the recrystallization operation, in order to obtain a silanol composition with high transparency, the cooling temperature is set to 10 From the viewpoint of improving the yield of cyclic silanol, the amount (volume) of the poor solvent is preferably The amount is preferably equal to or more than the amount of the good solvent and 20 times or less.

[0065] Examples of good solvents include tetrahydrofuran, diethyl ether, acetone, and methano. alcohol, ethanol, isopropanol, dimethylformamide, dimethyl sulfoxide, Examples of good solvents include glycerin, ethylene glycol, and methyl ethyl ketone. may be used alone or in combination of two or more.

[0066] Examples of poor solvents include toluene, chloroform, hexane, dichloromethane, and xylene. These poor solvents may be used alone or in combination of two or more. It may also be used.

[0067] In addition to the above-described method, the cyclic silanol used in the preparation of the silanol composition of the present embodiment can also be prepared by the following method: For example, in the presence of water or alcohol, Pd / carbon or the like is used to produce the hydrochloride represented by formula (10). It can also be synthesized by oxidizing a silane compound.

[0068] [ka]

[0069] Regarding the cyclic hydrosilane compound represented by formula (10) synthesized by the above method, The four types of hydroxyl groups represented by formulas (11) to (14) are derived from the arrangement of the organic group R and SiH groups on silicon. There are a mixture of stereoisomers of the same type. For example, 1,3,5,7-tetramethylcyclotetrasiloxane About Sun, Organometallics 1984, Vol.3, No.7 , pp1070-1075. 1In the measurement of H-NMR, the formulas (11) to (14 ) are calculated to be present at 11%, 27%, 52%, and 11%, respectively. .

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] When preparing cyclic silanols by oxidation of cyclic hydrosilane compounds, the oxidation product The proportion of the cyclic silanols (B1) to (B4) in the silanol composition is determined by the formula ( 10) in the cyclic hydrosilane compound represented by the formulas (11) to (14) For example, in the presence of water, 1,3,5,7-tetramethylsilyl On the silanol compositions obtained by oxidation of chlorotetrasiloxane using Pd / carbon. 1 When H-NMR was measured, the ratio of the cyclic silanols (B1) to (B4) was 9 %, 25%, 51%, and 15%, and the stereoisomers derived from the raw material cyclic hydrosilane compound The composition reflects the abundance ratio of the molecules.

[0075] The compound represented by formula (1) was obtained by oxidizing a hydrosilane compound using Pd / carbon or the like. The cyclic silanol represented by the formula (x), (y), and (z) is converted into the above stereoisomer. It is possible to adjust the ratio of isomers present, but the metal salt of cyclic silanol represented by formula (9) In the above-mentioned method using as an intermediate, it is easy to suppress the proportion of cyclic silanol (B2). This can be easily carried out, and the silanol composition of the present embodiment can be produced more efficiently. In addition, in the production method using the metal salt of cyclic silanol represented by formula (9) as an intermediate, There is no need to use a transition metal catalyst, and no transition metals remain, so irradiation with a low-pressure mercury lamp, etc. This can suppress discoloration caused by the

[0076] As described above, the silanol composition of this embodiment is formed by reacting an acid with a cyclic silanol. and isomerizing the silanol composition by adding a poor solvent to the good solvent solution. After recrystallization and filtration, the soluble solution obtained by filtration is concentrated to produce a suitable product. It is made.

[0077] In the production of the silanol composition of this embodiment, the solution of the soluble portion may be optionally concentrated. Alternatively, the solution of the soluble portion itself may be used as the silanol composition. In the concentration of the solution, it is not necessary to remove all of the solvent contained in the solution. The silanol composition is a crude concentrate obtained by distilling off a portion of the solvent contained in the soluble fraction solution. Furthermore, the silanol composition of the present embodiment may be prepared by concentrating a solution of the soluble portion. The solution may be diluted again with a solvent after the solution is prepared. One is a silanol composition containing a solvent.

[0078] The amount of the solvent in the solvent-containing silanol composition is not particularly limited. It is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total amount of the composition. The lower limit of the amount of the solvent is not particularly limited, but It is usually 1% by mass or more.

[0079] The solvent in the solvent-containing silanol composition may be water and / or alcohol used in the reaction. Examples of solvents include coal, good solvents and poor solvents used during recrystallization. Although not limited thereto, specific examples include water, tetrahydrofuran, diethyl ether, and Cetone, methanol, ethanol, isopropanol, dimethylformamide, dimethyl Sulfoxide, glycerin, ethylene glycol, methyl ethyl ketone, toluene, chloro Examples of the solvent include chloroform, hexane, dichloromethane, and xylene. They may be used alone or in combination of two or more.

[0080] (cured product) The cured product of this embodiment is obtained by curing the silanol composition of this embodiment. That is, one aspect of this embodiment is a cured product of the silanol composition of this embodiment.

[0081] The cured product of the present embodiment can be obtained by curing, i.e., by adding the silanol composition of the present embodiment to the cured product. The silanol groups (-Si-OH) contained in the polymer undergo a dehydration condensation reaction to form siloxane bonds (-Si The cured product of this embodiment is obtained by forming a tetra-O-Si- group. It is insoluble in solvents such as hydrofuran and toluene.

[0082] One embodiment of the present invention is a method for curing the silanol composition of the present invention. Lanol ​​may be polymerized in the absence of a catalyst or with the addition of a catalyst.

[0083] The catalyst used for the polymerization of cyclic silanols is a catalyst that induces the hydrolysis and condensation reaction of cyclic silanols. The catalyst can be an acid catalyst or an alkali catalyst. .

[0084] The acid catalyst is not particularly limited, but examples thereof include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, and chromic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, monochloroacetic acid, dichloroacetic acid Acid, trichloroacetic acid, trifluoroacetic acid, oxalic acid, malonic acid, sulfonic acid, phthalic acid, Fumaric acid, citric acid, maleic acid, oleic acid, methylmalonic acid, adipic acid, p-amino Suitable examples include p-benzoic acid and p-toluenesulfonic acid.

[0085] The alkali catalyst is not particularly limited, but examples thereof include sodium hydroxide and potassium hydroxide. Sodium bicarbonate, sodium carbonate, ammonium carbonate, ammonium bicarbonate, Suitable examples include aqueous ammonia and organic amines. When an inorganic base is used, In the present invention, a composition for forming an insulating film that does not contain metal ions is used.

[0086] The acid catalyst and the alkali catalyst may each be used alone or in combination of two or more. They may also be used in combination.

[0087] The amount of catalyst added can be adjusted depending on the reaction conditions. The amount of cyclic silanol added is preferably 0.000001 to 2 moles relative to the amount of cyclic silanol added. When the concentration exceeds 2 moles per mole of acid group, the reaction rate is very fast even at low concentrations, so the molecular It is difficult to control the amount and tends to gel easily.

[0088] When obtaining a cured product, the silanol composition is cured using an acid catalyst and an alkali catalyst. Specifically, the silanol composition can be subjected to a stepwise hydrolysis and condensation reaction. After the hydrolysis and condensation reaction is carried out with a base, the reaction is carried out again with a base, or the reaction is carried out first with a base. A cured product can be obtained by carrying out hydrolysis and condensation reaction, and then reacting again with an acid. Alternatively, a silanol composition may be prepared by reacting each of the compounds with an acid catalyst and an alkali catalyst and then mixing the condensates. It can also be used as.

[0089] (Method of curing silanol composition) The silanol composition of this embodiment may be heated when cured. The temperature at which the curing is carried out is not particularly limited, but in order to maintain the shape of the cured product, it is preferable to use a temperature of 6 The temperature is 0 to 250°C, and more preferably 80 to 200°C. A method for heat-curing the silanol composition of the embodiment, wherein the curing temperature is 60 to 250°C. That is the method.

[0090] In the method for curing the silanol composition of this embodiment, the shape of the cured product is maintained. Therefore, it is preferable to heat cure it for 10 minutes to 48 hours.

[0091] (glue) The silanol composition of the present embodiment can be used as an adhesive. One of the present embodiments is an adhesive containing the composition of the present embodiment. The composition is applied to a substrate to form an adhesive layer, and the adhesive layer containing the silanol composition is cured. The substrates are glass, silicon wafer, SiO2 wafer, S Examples include iN wafers and compound semiconductors. [Example]

[0092] The present invention will be explained in more detail using examples and comparative examples. The present invention and the following examples and comparative examples are not limited to the above. The methods for measuring the physical properties and evaluating the characteristics of the silanol composition are as follows.

[0093] (The mass percentage of cyclic silanol and its dehydration condensate in the silanol composition containing the solvent) (Calculation of cation concentration) The ECZ400S manufactured by JEOL Ltd. and the TFH probe were used, and the following By performing NMR measurements at the same temperature, the cyclic silanols in the silanol composition containing the solvent were The mass percent concentrations of the ethanol and its dehydrated condensates can be calculated. The silanol composition may be, for example, tetrahydroxytetramethyltetracyclosiloxane. and in the case of an isopropanol solution of its dehydrated condensation product, 0.1g of isopropanol solution of tetracyclosiloxane and its dehydrated condensate in deuterated acetone Using a sample spiked with 1g, 1 H-NMR was measured. Note that the base peak of the deuterated solvent was The measurement was performed with a concentration of 2.05 ppm and an accumulation count of 64. Tetrahydroxytetramethyltetracyclosiloxane and its dehydration condensation products by mass The cent concentration can be approximately calculated using the following formula: Tetrahydroxytetramethyltetracyclosiloxane and its dehydration condensation products by mass Peak of methyl groups bonded to Si in the region of -0.1-0.3 ppm Integral ratio / 12×304.51) / {(-0.1-0.3 ppm region of metals bonding to Si Peak integral ratio of ethyl group / 12 × 304.51) + (isopropyl group in the 3.7-4.1 ppm region) Peak integral value of hydrogen bonded to carbon of propanol / 1 × 60.1) In the above formula, 304.51 is tetrahydroxytetramethyltetracyclosiloxane 60.1 means the molecular weight of isopropanol.

[0094] (Haze measurement) Haze was measured using a turbidity meter NDH5000W (manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K7136. The specific procedure is as follows: The haze of the silanol composition was measured on a plain glass substrate 5cm x 5cm x 0.7mm thick (Technoprint A 42 wt% isopropanol solution of silanol compound was applied to a bar coater No. After coating with 0 (manufactured by AS ONE), the film was dried under reduced pressure at 60°C for 1 hour, and the haze was measured. The blank for haze measurement is a plain glass substrate 5cm x 5cm x 0.7mm thick (Technoprint). Only cellulose acetate (manufactured by Toshiba) was used. The haze of the cured product was measured by measuring the haze of the silanol composition by measuring the haze of the sample at 100 The measurement was carried out using a sample obtained by heating at 2°C for 2 hours.

[0095] (Film thickness measurement) The film thickness was measured by measuring the haze using a surface profiler (manufacturer: Kosaka Co., Ltd.). Measurements were taken using a laboratory model ET4000AK31, and the film thickness was calculated.

[0096] (Measurement of light transmittance of silanol composition at 265 nm) The light transmittance was measured using a spectrophotometer U-4100 (Hitachi High-Technologies Corporation). The specific steps are shown below. The light transmittance of the silanol composition at 265 nm was For the propanol solution, a quartz glass cell 10 x 4 x 45H (Tokyo Glass Instruments Co., Ltd.) was used. The blank for light transmittance was a quartz glass cell 10x4x45H (Tokyo Glass Co., Ltd.). Only the instrument manufactured by Kikaisha was used.

[0097] ( 1 Calculation of stereoisomeric ratio of cyclic silanols using H-NMR measurements The ECZ400S manufactured by JEOL Ltd. and the TFH probe were used, and the following NMR measurements were carried out. 1 g of deuterated acetone was added to 0.1 g of the obtained silanol composition, 1 Measure H-NMR The reference peak of the heavy solvent was set at 2.05 ppm, and the measurement was performed with 64 integrations. . Tetramethyltetracyclosiloxane was used as a hydrosilane compound and oxidized. When the tetrahydroxytetramethyltetracyclosiloxane obtained is 1 H-NM In R, six types of Si bonds originating from four types of isomers are found in the 0.04-0.95 ppm range. The peaks of the associated methyl groups were observed. The hydrogen atoms of the methyl groups are, from the high magnetic field side, all-cis (0.057 ppm), tran s-trans-cis type (0.064ppm), trans-trans-cis type ( 0.067ppm), cis-trans-cis type (0.074ppm), all-t rans type (0.080ppm), trans-trans-cis type (0.087pp The six peaks were observed in the order of m). Waveform separation was performed using the Lorentz transform for these hydrogen peaks, and the ring-shaped The proportions of each stereoisomer of Lanol ​​were calculated.

[0098] (Preparation of each stereoisomer) All-cis (cyclic silanol (B1)) Inorganic Chemistry Volume 49, Issue 2, It was synthesized according to the synthetic method described on pages 572-577. cis-trans-cis (cyclic silanol (B2)) European Pol ymer Journal 2012, Vol.48, 1073-1081 It was synthesized according to the synthesis method. All-trans isomer (cyclic silanol (B4)) Tetrahydrofuran and dichloromethane containing 10 wt% silanol prepared in Comparative Example 6 The mixed solution was further concentrated until the silanol content was 20 wt %. The stereoisomers were separated using chromatography. <Liquid chromatography conditions> Equipment: GL Science liquid chromatography Pump: PU715 Column oven: CO705 Fraction collector: FC204YMC-PackSIL-06 φ30mm× 250mm Eluent: Cyclohexane / EtOAc =60 / 40 Flow rate: 40mL / min Injection volume: 5mL Temperature: 40℃ Detection: The obtained fractions were evaluated by ELSD measurement and detected. Ta. The eluate of the all-trans isomer obtained was allowed to stand, and the all-trans isomer crystallized. was obtained and recovered by filtration. trans-trans-cis isomer (cyclic silanol (B3)) The eluate obtained in the same manner as for the all-trans isomer was concentrated and then placed in isopropanol. obtained by exchanging

[0099] (Measurement of Area Percentages of Cyclic Silanol (A1) and Dehydration Condensate (A2) by GPC) Dissolve 0.03g of silanol compound in 1.5mL of tetrahydrofuran. The resulting solution was used as a measurement sample. This measurement sample was used for measurement using a Tosoh HLC-8220GPC. The columns were TSK guard column SuperH-H and TSKgel Super rHM-H, TSKgel SuperHM-H, TSKgel SuperH2000 TSKgel SuperH1000 was connected in series to The mobile phase was analyzed at a rate of 0.35 ml / min. The detector used was an RI detector, and the detector was manufactured by the American Polymer Stand. Polymethyl methacrylate standard sample (molecular weight: 210) manufactured by ARDS Corporation 0000, 322000, 87800, 20850, 2000, 670000, 1300 00, 46300, 11800, 860), and 1,3,5,7-tetramethylcyclotetramethyl Using trasiloxane (molecular weight 240.5, manufactured by Tokyo Chemical Industry Co., Ltd.) as a standard substance, the number average molecular weight and The weight average molecular weight was determined, and the peaks of p=0 and p≧1 were identified to identify the cyclic silanol (A1). The area ratio of the peaks of the dehydrated condensation product (A1) and the dehydrated condensation product (A2) was calculated.

[0100] (Check adhesive strength) The T-3000-FC3 manual was placed on the sample prepared for haze measurement of the silanol composition. A hemispherical quartz lens with a diameter of 2 mm was bonded to the bonded surface with a load of 40°C using a dual die bonder (TRESKY). After that, the hemispherical lens was heated at 100°C for 2 hours under normal pressure. The glass with the adhesive on it was pressed from the side to check whether it was adhered.

[0101] (Check for discoloration before and after exposure to a low-pressure mercury lamp) The sample prepared for haze measurement of the silanol composition was subjected to a low-pressure mercury lamp. The UV ozone irradiation device manufactured by Tasen Special Light Source Co., Ltd. was used to irradiate the product for 6 hours. I checked whether it was available or not.

[0102] [Example 1] In a reaction vessel, all-cis 1,3,5,7-tetrahydroxy-1,3,5,7 -Tetramethyltetracyclosiloxane (hereinafter also referred to as D4OH) 0.3 g, tetramethyltetracyclosiloxane Add 8 mL of trihydrofuran (hereinafter referred to as THF, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and mix. In addition, all-cis 1,3,5,7-tetrahydroxy-1,3,5,7 -Tetramethyltetracyclosiloxane is an Inorganic Chemistry Prepared according to the method described in Volume 49, Issue 2, P572-577 2 mL of 1 mol / L acetic acid aqueous solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel. The reaction mixture was neutralized by adding saturated aqueous sodium bicarbonate solution. After that, the organic layer was collected using a separating funnel and washed twice with saturated saline. After washing, the organic layer was dried using magnesium sulfate and filtered using a pleated filter paper. The sodium was filtered off, and the filtrate was concentrated using an evaporator to obtain 2 g of D4OH concentrate. Furthermore, isopropanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and the mixture was concentrated again. A silanol composition (isopropanol solution) of a given concentration was prepared. The haze of the obtained silanol composition was measured according to the method described above (Haze Measurement). The peak area in the differential molecular weight distribution curve of GPC was measured. The stereoisomer ratio of Lanol ​​is 1 Calculated by H-NMR measurement. 1 H-NMR spectrum Tor.

[0103] [Example 2] trans-trans-cis D4O instead of all-cis D4OH The silanol was synthesized in the same manner as in Example 1, except that H was used as the raw material and the reaction time was 1 hour. A composition was prepared.

[0104] [Example 3] Instead of all-cis D4OH, all-trans D4OH is used as a raw material. A silanol composition was prepared in the same manner as in Example 1, except that the reaction time was changed to 2 hours. did.

[0105] [Example 4] In a reaction vessel, all-cis 1,3,5,7-tetrahydroxy-1,3,5,7 -Tetramethyltetracyclosiloxane (hereinafter also referred to as D4OH) 0.3 g, TH 8 mL of 1 mol / L acetic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel and mixed. 2 mL of an aqueous acid solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and the mixture was stirred at room temperature for 3.5 hours. After neutralizing the liquid by adding saturated aqueous sodium bicarbonate solution, the organic layer was collected using a separatory funnel. The organic layer is washed twice with saturated saline. After washing, the organic layer is added with magnesium sulfate. The filtrate was evaporated in an evaporator. Concentration gave 2 g of D4OH concentrate (THF solution). Subsequently, this concentrate was added to a mixed solvent of 14 mL of THF and 1 mL of dichloromethane. The mixture was left to stand at 5°C for 4 hours, and then the precipitated insoluble matter was removed by filtration under reduced pressure. The filtrate was concentrated using a condenser to a THF solution containing 10 wt % of the silanol composition. Then, isopropanol is added, and the mixture is concentrated again to obtain a silanol composition (isopropanol) of a predetermined concentration. A propyl alcohol solution was prepared. The obtained silanol composition was evaluated for physical properties such as haze. The stereoisomer ratio of 1 Calculation was performed by H-NMR measurement.

[0106] [Example 5] Instead of the all-cis form of D4OH, European Polymer Jou The method was based on that described in International Journal of Biomedical Engineering (2012), Vol. 48, 1073-1081. The synthesized cis-trans-cis D4OH was used as a raw material, and 1 mol / L acetic acid was added to 5 ml The same procedure as in Example 4 was repeated except that 1 L of silanol compound was used and the reaction time was 1 hour. was produced.

[0107] [Example 6] trans-trans-cis D4O instead of all-cis D4OH The same procedure as in Example 4 was carried out except that H was used as the raw material and the reaction time was 1 hour. A composition was prepared.

[0108] [Example 7] Instead of all-cis D4OH, all-trans D4OH is used as a raw material. A silanol composition was prepared in the same manner as in Example 4, except that the reaction time was changed to 2 hours. did.

[0109] [Example 8] In a reaction vessel, all-cis 1,3,5,7-tetrahydroxy-1,3,5,7 -Tetramethyltetracyclosiloxane (hereinafter also referred to as D4OH) 0.3 g, TH 8 mL of 1 mol / L acetic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction vessel and mixed. 5 mL of an aqueous acid solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 1 hour. After neutralizing the mixture by adding saturated aqueous sodium bicarbonate, the organic layer was collected using a separatory funnel. The collected organic layer is washed twice with saturated saline. After washing, magnesium sulfate is added to the organic layer. The magnesium sulfate was filtered off using a pleated filter paper. The filtrate was concentrated in an evaporator. As a result, 2 g of D4OH concentrate (THF solution) was obtained. Next, this concentrate was mixed with 14 mL of THF and 1 mL of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd.). The mixture was left to stand at 5°C for 4 hours, and the precipitated insoluble matter was filtered off. The filtrate was evaporated to a THF solution containing 10 wt% of the silanol compound. Furthermore, isopropanol (Fujifilm Wako Pure Chemical Industries, Ltd.) was added and the mixture was concentrated again. Concentration was carried out to prepare a silanol composition (isopropanol solution) of a predetermined concentration. The obtained silanol composition was evaluated for physical properties such as haze. The stereoisomer ratio of 1 The results were calculated by H-NMR measurement. The sample was then irradiated with a low-pressure mercury lamp for 6 hours, and the presence or absence of discoloration was confirmed.

[0110] [Comparative Example 1] The all-cis form (cyclic silanol (B1)) prepared in the above (Preparation of each stereoisomer) ) to prepare a 5% concentration silanol composition (isopropanol solution), The resulting composition was a 100% ethanol composition.

[0111] Comparative Example 2 The cis-trans-cis isomer (cyclic silanolate) prepared in the above (preparation of each stereoisomer) Prepare a 5% silanol solution (isopropanol solution) using silanol (B2). This was used to prepare a silanol composition.

[0112] Comparative Example 3 The all-trans isomer (cyclic silanol (B 4)) to prepare a 5% concentration silanol composition (isopropanol solution), and The composition was a kol composition.

[0113] Comparative Example 4 The trans-trans-cis isomer (cyclic cyclohexyl isomer) prepared in the above (Preparation of each stereoisomer) Silanol (B3)) was used to prepare a 5% concentration silanol composition (isopropanol solution). A silanol composition was prepared.

[0114] Comparative Example 5 The concentrated D4OH-containing THF solution was added to a mixed solvent of THF and dichloromethane. The mixture was left to stand at 5°C for 4 hours, and the precipitated insoluble matter was removed by filtration. The same experiment as in Example 8 was carried out except that:

[0115] Comparative Example 6 (Preparation of Silanol Composition) The concentrated D4OH-containing THF solution was added to a mixed solvent of THF and dichloromethane. The mixture was cooled to 4°C for 1 hour without recrystallization. a Polymer Journal 2012, Vol.48, P1073-1 The silanol composition was synthesized according to the method described in 081. The obtained silanol composition was used to measure haze and other issues. The cured composition was irradiated with a low-pressure mercury lamp for 6 hours to evaluate discoloration. We checked whether or not there was any problem.

[0116] The physical properties and evaluation results of the silanol compositions and cured products obtained in the examples and comparative examples are shown in Tables 1 and 2. and Table 2.

[0117] [Table 1]

[0118] [Table 2] However, when the curable composition containing all-cis tetrahydroxytetramethyltetracyclosiloxane disclosed in Non-Patent Document 1 is applied to an object to be protected, sealed, or bonded, there is a problem that sufficient adhesive strength is not obtained. Furthermore, when cyclic silanols and compositions containing such cyclic silanols are applied to optical materials such as lenses, transparency is required when the cyclic silanols and compositions containing such cyclic silanols are cured. Therefore, an object of the present embodiment is to provide a silanol composition having excellent adhesive strength and transparency. Here, "adhesive strength" refers to adhesive strength when cured, and "transparency" encompasses both transparency in the form of the composition and transparency in the form of the cured composition. As a result of intensive research into solving the above-mentioned problems, the present inventors discovered that the above-mentioned problems can be solved by adjusting the ratio of each stereoisomer of cyclic silanol to a specific range, thereby completing the present invention. That is, this embodiment is as follows. [1] Cyclic silanol (A1) represented by the following formula (1): [ka] (In formula (1), R 1 ~R 4 are each independently a fluorine atom, an aryl group, a vinyl group, an allyl group, a linear or branched alkyl group having 1 to 4 carbon atoms and substituted with fluorine, or an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, The cyclic silanol (A1) is cyclic silanol (B1) to (B4) represented by the following formulas (2) to (5): [ka] [ka] [ka] [ka] (In formulas (2) to (5), R 1 ~R 4 are each independently a fluorine atom, an aryl group, a vinyl group, an allyl group, a linear or branched alkyl group having 1 to 4 carbon atoms and substituted with fluorine, or an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, When the proportions (mol %) of the cyclic silanols (B1), (B3), and (B4) relative to the total amount of the cyclic silanols (B1) to (B4) are a, c, and d, respectively, the following conditions (x), (y), and (z) are satisfied: (x)75≦a+c<100 (y)75≦c+d<100 and 25 <d<100 (z)60≦c<100 The silanol composition satisfies at least one selected from the group consisting of: [2] When the ratio (mol %) of the cyclic silanol (B2) to the total amount of the cyclic silanols (B1) to (B4) is represented by b, the following condition (w) is satisfied: (w)0 <b≦20 fulfill, [1] The silanol composition according to [1]. [3] The haze at a thickness of 3 μm is 10% or less. The silanol composition according to [1] or [2]. [4] Does not contain transition metals The silanol composition according to any one of [1] to [3]. [5] containing a dehydration condensate (A2) of a cyclic silanol (A1), the area of ​​the dehydrated condensate (A2) is more than 0% and not more than 50% of the total area of ​​the cyclic silanol (A1) and the dehydrated condensate (A2) as measured by gel permeation chromatography; The silanol composition according to any one of [1] to [4]. [6] The light transmittance at a wavelength of 265 nm at a thickness of 3 μm is 80% or more. The silanol composition according to any one of [1] to [5]. [7] containing a solvent, The silanol composition according to any one of [1] to [6]. [8] A cured product of the silanol composition according to any one of [1] to [7]. [9] An adhesive comprising the silanol composition according to any one of [1] to [7]. According to this embodiment, a silanol composition having excellent adhesive strength and transparency can be provided. [Industrial Applicability]

[0119] The silanol composition of the present invention is useful for protecting, sealing, and Adhesion, changing or adjusting the wavelength of light emitted from light-emitting diode elements, and lenses, etc. Furthermore, the silanol composition of the present invention has industrial applicability in the fields of Lens materials, optical devices, materials for optical components, display materials, and various other optical materials, electronic materials, Industrially applicable in the fields of electronic devices, insulating materials for electronic components, coating materials, etc. It has sexuality.

Claims

1. Cyclic silanol (A1) represented by the following formula (1): 【Chemistry 1】 (In formula (1), R 1 ~R 4 and each independently represent a fluorine atom, an aryl group, a vinyl group, an allyl group, a fluorine-substituted linear or branched alkyl group having 1 to 4 carbon atoms, or an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms), with a weak acid in the presence of water; a step of removing crystalline precipitates by adding a poor solvent or cooling the solution of the obtained product in a good solvent after the step of reacting with the weak acid, thereby obtaining a solution of the soluble portion; A method for producing a silanol composition comprising:

2. The method for producing a silanol composition according to claim 1, wherein the cyclic silanol (A1) is a single isomer or a mixture of isomers.

3. 3. The method for producing a silanol composition according to claim 2, wherein the cyclic silanol (A1) includes an all-cis type, a cis-trans-cis type, a trans-trans-cis type, or an all-trans type.

4. The haze of the silanol composition at a thickness of 3 μm is 10% or less. A method for producing the silanol composition according to any one of claims 1 to 3.

5. The silanol composition comprises cyclic silanols (B1) to (B4) represented by the following formulas (2) to (5): 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 (In formulas (2) to (5), R 1 ~R 4 are each independently a fluorine atom, an aryl group, a vinyl group, an allyl group, a linear or branched alkyl group having 1 to 4 carbon atoms and substituted with fluorine, or an unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms; When the proportions (mol %) of the cyclic silanols (B1), (B3), and (B4) relative to the total amount of the cyclic silanols (B1) to (B4) are a, c, and d, respectively, the following (x) 75≦a+c<100 (y) 75≦c+d<100 and 25<d<100 (z)60≦c<100 The method for producing a silanol composition according to any one of claims 1 to 4, wherein at least one selected from the group consisting of:

6. When the ratio (mol %) of the cyclic silanol (B2) to the total amount of the cyclic silanols (B1) to (B4) is represented by b, the following condition (w) is satisfied: (w) 0<b≦20 fulfill, A method for producing the silanol composition according to claim 5.

Images